WO2023202486A1 - 烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统 - Google Patents

烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统 Download PDF

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WO2023202486A1
WO2023202486A1 PCT/CN2023/088407 CN2023088407W WO2023202486A1 WO 2023202486 A1 WO2023202486 A1 WO 2023202486A1 CN 2023088407 W CN2023088407 W CN 2023088407W WO 2023202486 A1 WO2023202486 A1 WO 2023202486A1
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carbon dioxide
solid waste
mineralization
industrial solid
flue gas
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PCT/CN2023/088407
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English (en)
French (fr)
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高铭
赵黄经
周小舟
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瀜矿环保科技(上海)有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B01J6/008—Pyrolysis reactions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/24—Magnesium carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/602—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/606—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • This application belongs to the fields of hydrometallurgical technology, carbon dioxide capture, utilization and storage (Carbon Capture, Utilization and Storage), and solid waste resource utilization, specifically involving carbon dioxide capture in flue gas and carbon dioxide mineralization coupling system based on industrial solid waste .
  • CO 2 capture technology based on the principle of calcium cycle is mostly focused on the capture of carbon dioxide in the flue gas of cement or lime plants. However, it is aimed at the capture of carbon dioxide in the flue gas of steel plants and the coupling with related production lines such as steel plants. Still a blank field.
  • the absorption capacity of calcium oxide (CaO) will decrease sharply. After the number of cycles reaches a certain level, the deactivated CaO cannot continue to serve as an efficient CO 2 adsorbent.
  • the disposal method of deactivated CaO is also a difficult problem.
  • deactivated CaO can be added to raw materials for cement firing; however, in other industry application scenarios, there is a lack of better utilization of deactivated CaO. Way. Therefore, in order to maintain a high CO 2 capture efficiency without causing secondary pollution, the usual calcium recycling method requires a calcium-based adsorption method that has high absorption capacity and recycling efficiency and produces waste without causing secondary pollution to the environment. agent, the price of this type of high-performance calcium-based adsorbent is generally It is often difficult for enterprises to accept it. If the cost of the adsorbent is considered and traditional adsorbents are used, it will lead to problems such as low capture efficiency, large waste production and difficulty in treatment. Therefore, the efficiency and cost of carbon dioxide capture in flue gas using the calcium cycle method have always been challenges faced by the industry.
  • the technical problem to be solved by this application is to provide a coupling system for carbon dioxide capture in flue gas and carbon dioxide mineralization based on industrial solid waste.
  • This application proposes a coupling system for carbon dioxide capture in flue gas and carbon dioxide mineralization based on industrial solid waste, including:
  • An adsorption reaction device the flue gas is input into the adsorption reaction device and undergoes an adsorption reaction with the adsorbent built in the adsorption reaction device, and generates a first carbonate product;
  • Thermal decomposition device the first carbonate product generates oxides and carbon dioxide after thermal decomposition treatment by the thermal decomposition device;
  • the oxides are returned to the adsorption reaction device for cyclic reaction; after multiple cyclic reactions, the deactivated and scrapped oxides are transported to the industrial solid waste mineralization system to participate. Reaction; the carbon dioxide is transported to the industrial solid waste mineralization system to participate in the reaction.
  • the above-mentioned coupling system of carbon dioxide capture in flue gas and carbon dioxide mineralization based on industrial solid waste wherein the second carbonate product prepared by the industrial solid waste mineralization system can be partially recycled to the thermal decomposition
  • the device continues thermal decomposition to form new adsorbent to supplement the deactivated and discarded oxides.
  • the above-mentioned coupling system for carbon dioxide capture in flue gas and carbon dioxide mineralization based on industrial solid waste also includes: a water conduction device matching the arrangement of the adsorption reaction device, and the water conduction device is used to collect all the carbon dioxide. The heat of the adsorption reaction device.
  • the above-mentioned coupling system of carbon dioxide capture in flue gas and carbon dioxide mineralization based on industrial solid waste, wherein the heat transfer water in the water transfer device reacts with the scrapped oxide to generate hydrogen.
  • the oxide, the hydroxide and the carbon dioxide produced by decomposition of the thermal decomposition device participate in the mineralization reaction of the industrial solid waste mineralization system.
  • the above-mentioned coupling system of carbon dioxide capture in flue gas and carbon dioxide mineralization based on industrial solid waste wherein the heat source of the thermal decomposition device adopts traditional fossil fuels, solar energy, wind energy and other sustainable energy sources, nuclear energy or steel slag recycling residual heat.
  • the above-mentioned coupling system of carbon dioxide capture in flue gas and carbon dioxide mineralization based on industrial solid waste in which carbon dioxide produced by traditional fossil fuel combustion is collected and input into the adsorption reaction device to participate in the adsorption reaction.
  • the above-mentioned coupling system of carbon dioxide capture in flue gas and carbon dioxide mineralization based on industrial solid waste wherein the adsorbent includes: oxides produced by thermal decomposition of the first carbonate product, the second carbonic acid Oxides produced by thermal decomposition of salt products, natural calcium-based adsorbents, natural magnesium-based adsorbents or alkaline industrial solid waste.
  • the above-mentioned coupling system of carbon dioxide capture in flue gas and carbon dioxide mineralization based on industrial solid waste also includes: a desulfurization device and/or a denitrification device; the flue gas passes through the desulfurization device and/or Or after desulfurization and denitration treatment by the denitrification device, it is transported to the adsorption reaction device.
  • the above-mentioned coupling system of carbon dioxide capture in flue gas and carbon dioxide mineralization based on industrial solid waste wherein the industrial solid waste mineralization system includes: a mixing reaction device and a solid-liquid separation device, wherein the deactivation and scrapping The oxides and the carbon dioxide generated by decomposition of the thermal decomposition device are transported to the mixing reaction device to participate in the reaction; the solid-liquid separation device is used to perform solid-liquid separation on the slurry reacted by the mixing reaction device. , the unreacted solid particles obtained from solid-liquid separation will be recycled to the next stage of reaction and separation.
  • the industrial solid waste mineralization system includes: a mixing reaction device and a solid-liquid separation device, wherein the deactivation and scrapping The oxides and the carbon dioxide generated by decomposition of the thermal decomposition device are transported to the mixing reaction device to participate in the reaction; the solid-liquid separation device is used to perform solid-liquid separation on the slurry reacted by the mixing reaction device. , the unreacted solid particles obtained from solid
  • the above-mentioned coupling system of carbon dioxide capture in flue gas and carbon dioxide mineralization based on industrial solid waste wherein the industrial solid waste mineralization system also includes: a product preparation device based on separation by the solid-liquid separation device The second carbonate product is prepared from the final clear liquid, and the second carbonate product is partially recycled to the thermal decomposition device and undergoes thermal decomposition treatment to supplement the deactivated and discarded oxides.
  • the above carbon dioxide capture in flue gas is coupled with carbon dioxide mineralization based on industrial solid waste.
  • a combined system wherein the first carbonate product includes: calcium carbonate, magnesium carbonate or calcium magnesium carbonate; and/or the second carbonate product includes: calcium carbonate, magnesium carbonate or calcium magnesium carbonate.
  • This application can couple CO 2 capture in flue gas with a CO 2 mineralization system based on industrial solid waste, in which the concentrated carbon dioxide and deactivated scrapped oxides generated during the carbon dioxide capture process in flue gas can be used to produce high-quality
  • the raw materials required for high-quality carbonates coupling the two processes not only realize the capture and utilization of carbon dioxide, but also realize the reuse of waste; while producing high-quality chemical products, the carbon dioxide capture production line in flue gas also It is easy to be organically combined with the production line of the carbon dioxide mineralization system based on industrial solid waste, which expands the selection range and acquisition methods of carbon dioxide sources for the carbon dioxide mineralization system based on industrial solid waste, and reduces the cost of carbon dioxide concentration and industrial solid waste. Waste carbon dioxide mineralization process costs.
  • the second carbonate product prepared by the industrial solid waste mineralization system in this application can be partially recycled to the thermal decomposition device for thermal decomposition again to supplement the deactivated and discarded oxides, thereby forming a dual circulation system.
  • This recycling process can make full use of the calcium and magnesium elements in the existing industrial solid waste to achieve resource reuse; and the double-cycle process can ensure the continuity of the reaction process, improve reaction efficiency, and optimize The combined cost of carbon dioxide capture and utilization.
  • the water-conducting device in this application can absorb the waste heat of the adsorption reaction device and use it as a partial heat source for the industrial solid waste mineralization system, without wasting the heat-conducting water, which is energy-saving and economical.
  • This application can realize the recycling of solid waste and carbon dioxide resources, can achieve green regeneration, can control the material consumption and energy consumption of additional inputs, generate almost no secondary pollution, can achieve carbon emission reduction and utilization, and is green and environmentally friendly.
  • Figure 1 Carbon dioxide capture in flue gas and carbon dioxide based on industrial solid waste according to one embodiment of this application Flow chart of mineralization coupling system
  • Figure 2 Flow chart of a coupling system for carbon dioxide capture in flue gas and carbon dioxide mineralization based on industrial solid waste according to another embodiment of the present application;
  • Figure 3 Flow chart of the industrial solid waste mineralization system in one embodiment of the present application.
  • a coupling system for carbon dioxide capture in flue gas and carbon dioxide mineralization based on industrial solid waste includes:
  • Adsorption reaction device 20 the flue gas 10 is input into the adsorption reaction device 20 and undergoes an adsorption reaction with the adsorbent built in the adsorption reaction device 20, and generates a first carbonate product;
  • Thermal decomposition device 30 the first carbonate product generates oxides and carbon dioxide after thermal decomposition treatment by the thermal decomposition device 30;
  • the oxides are returned to the adsorption reaction device 20 for circulation reaction; after multiple cycles of reaction, the deactivated and scrapped oxides are transported to the industrial solid waste mineralization system. 40 to participate in the reaction; the carbon dioxide is transported to the industrial solid waste mineralization system 40 to participate in the reaction.
  • the carbon dioxide capture method in flue gas can be coupled with the industrial solid waste mineralization system 40, that is, the capture and utilization of carbon dioxide can be achieved, and at the same time, production can be achieved. High-quality chemical products can be produced.
  • the production line for capturing carbon dioxide in flue gas can be easily combined with the production line of the industrial solid waste mineralization system 40, etc., resulting in a higher degree of industrialization.
  • the industrial solid waste involved in this embodiment includes but is not limited to: steel slag, ore raw materials or tailings.
  • the adsorbent can use oxides produced by thermal decomposition of the first carbonate product, oxides produced by thermal decomposition of the second carbonate product, natural calcium-based adsorbents, natural magnesium base adsorbent or alkaline industrial solid waste, wherein the natural calcium-based adsorbent includes but is not limited to: limestone, dolomite, etc.
  • the second carbonate product prepared by the industrial solid waste mineralization system 40 can be partially recycled to the thermal decomposition device 30 to continue thermal decomposition treatment. , undergo thermal decomposition treatment to replenish the deactivated and discarded oxides.
  • This embodiment adds another internal cycle process based on the above-mentioned Embodiment 1. This cycle process can make full use of the calcium and magnesium elements in the existing industrial solid waste to realize the reuse of resources; and the double cycle process can ensure the reaction process continuity, improve reaction efficiency, and optimize the overall cost of carbon dioxide capture and utilization.
  • the first carbonate product mentioned above includes: calcium carbonate, magnesium carbonate or calcium magnesium carbonate
  • the second carbonate product includes: calcium carbonate, magnesium carbonate or calcium magnesium carbonate
  • the core principle of the calcium cycle method to absorb CO 2 is to utilize the reversibility of the reaction between CaO and CO 2 to achieve a continuous cycle of carbonic acid/calcination.
  • the cycle reaction formula is:
  • it also includes: a desulfurization device (not shown in the figure). After the flue gas 10 is desulfurized by the desulfurization device, it is transported to the adsorption reaction device 20 .
  • a desulfurization device (not shown in the figure). After the flue gas 10 is desulfurized by the desulfurization device, it is transported to the adsorption reaction device 20 .
  • this embodiment also includes a denitrification device (not shown in the figure). After the flue gas 10 is denitrified by the denitrification device, it is transported to the adsorption reaction device 20 .
  • this embodiment is equipped with a desulfurization device and a denitrification device at the same time. After the flue gas 10 is processed by the desulfurization device and the denitrification device respectively, it is transported to the adsorption reaction device 20, wherein the desulfurization device and The order of the denitrification devices is not limited.
  • the adsorption reaction device 20 preferably adopts an adsorption tower, and further preferably, the adsorption reaction device 20 adopts a fluidized bed reactor.
  • the flue gas 10 enters the desulfurization device and/or the denitrification device into the adsorption reaction device 20 to perform a carbonation reaction with CaO to generate a CaCO 3 product, and the CaCO 3 product is transported to the thermal decomposition device 30 for thermal decomposition treatment.
  • the flue gas 10 enters the desulfurization device and/or the denitrification device into the adsorption reaction device 20 to perform a carbonation reaction with MgO to generate an MgCO 3 product, and the MgCO 3 product is transported to the thermal decomposition device. 30 for thermal decomposition treatment.
  • the flue gas 10 enters the desulfurization device and/or the denitrification device into the adsorption reaction device 20 and performs a carbonation reaction with calcium and magnesium oxide to generate a calcium magnesium carbonate product, and the calcium and magnesium carbonate product is transported to the The thermal decomposition device 30 performs thermal decomposition processing.
  • the flue gas 10 comes from power plant flue gas, steel plant blast furnace, converter, refining furnace, lime kiln flue gas, coal chemical industry tail gas or petrochemical industry tail gas.
  • the thermal decomposition device 30 preferably uses a high-temperature calcining furnace.
  • the preferred calcining temperature is 400-900°C.
  • the first carbonate product is subjected to high-temperature calcining treatment in the high-temperature calcining furnace to generate oxides and CO 2 .
  • the oxides generated by the reaction can return to the adsorption reaction
  • the reaction should be circulated in the device 20, and high-purity CO 2 can be efficiently absorbed under the actual exhaust gas temperature and pressure of the reaction, which facilitates transportation and storage after cooling, liquefaction and compression.
  • the deactivated and scrapped oxides can be transported to the industrial solid waste mineralization system 40 to participate in the mineralization reaction.
  • the specific reaction process involved above varies depending on the first carbonate product.
  • the CaCO 3 product is subjected to high-temperature calcining treatment in the high-temperature calcining furnace to generate CaO and CO 2 .
  • the CaO generated by the reaction can be returned to the adsorption reaction device 20 for circulation reaction, and high-purity CO 2 can be efficiently absorbed under the actual exhaust temperature and pressure of the reaction, which facilitates transportation and storage after cooling, liquefaction and compression.
  • the deactivated and scrapped CaO can be transported to the industrial solid waste mineralization system 40 to participate in the mineralization reaction of steel slag.
  • the MgCO 3 product is subjected to high-temperature calcination in the high-temperature calcination furnace to generate MgO and CO 2 .
  • the MgO generated by the reaction can be returned to the adsorption reaction device 20 for circulation reaction, and high-purity CO 2 can be efficiently absorbed under the actual exhaust gas temperature and pressure of the reaction, which facilitates transportation and storage after cooling, liquefaction and compression.
  • the deactivated and scrapped MgO can be transported to the industrial solid waste mineralization system 40 to participate in the mineralization reaction of steel slag.
  • the calcium magnesium carbonate product is subjected to high-temperature calcining in the high-temperature calcining furnace to generate calcium magnesium oxide and CO 2 .
  • the calcium and magnesium oxide generated by the reaction can be returned to the adsorption reaction device 20 for circulation reaction, and during the actual discharge of the reaction It can efficiently absorb high-purity CO 2 under the smoke temperature and pressure, which facilitates transportation and storage after cooling, liquefaction and compression.
  • the deactivated and scrapped calcium and magnesium oxide can be transported to the industrial solid waste mineralization system 40 to participate in the mineralization reaction of steel slag.
  • the absorption capacity of natural calcium-based adsorbents/magnesium-based adsorbents will decrease sharply after multiple cycles.
  • the following uses a natural calcium-based adsorbent as an example to explain its principle: when CaO is carbonated, CO 2 first diffuses to the particle surface for rapid reaction. At the same time, it penetrates through the pores on the particle surface and reacts with the larger pore surface. The above The process is the rapid reaction stage of chemical reaction control. Subsequently, the CaCO 3 product layer formed on the particle surface and the inner surface of the pores hinders the reaction of internal CaO and CO 2. When the product layer exceeds a critical thickness, the reaction enters the slow reaction stage controlled by product layer diffusion.
  • the adsorbent particles are repeatedly calcined at high temperatures, the crystal grains inside the particles fuse and grow, the surface area and pore volume of the adsorbent continue to decrease, and sintering occurs. As the number of cycles increases, the sintering phenomenon intensifies, the small pores decrease, the macropores increase, the crystal grains fuse with each other, and the adsorbent particles collapse, resulting in a continuous decline in absorption capacity. Therefore, deactivated CaO with too many cycles cannot continue to serve as an efficient CO 2 adsorbent. In order to maintain a high CO 2 capture efficiency, the usual calcium cycle method requires a calcium-based adsorbent with high absorption capacity and cycle efficiency, low price, and waste production that does not cause secondary pollution to the environment.
  • the partially failed or scrapped CaO can be transported to the industrial solid waste mineralization system 40 to participate in the mineralization reaction of steel slag, that is, the partially failed or scrapped CaO can be perfectly utilized; And it avoids the technical defects in the existing technology, such as the need for additional use of high-performance adsorbents such as modified CaO.
  • the heat source 50 of the thermal decomposition device 30 can use traditional fossil fuels, sustainable energy sources such as solar energy and wind energy, nuclear energy or steel slag to recover waste heat. If steel slag is used to recover waste heat, the useful resources of the industrial solid waste mineralization system 40 can be fully utilized, and resource reuse can be achieved to a greater extent.
  • the carbon dioxide generated by traditional fossil fuel combustion can be collected and input into the adsorption reaction device 20 to participate in the adsorption reaction
  • the traditional fuels include but are not limited to: natural gas, coal, oil, etc.
  • This embodiment also includes: a water conduction device (not shown in the figure) configured to match the adsorption reaction device 20 , and the water conduction device is used to collect heat from the adsorption reaction device 20 . Since the reaction between CaO and CO 2 and the reaction between MgO and CO 2 are both a strong exothermic reaction process, the heat released by the reaction can be utilized by the water conduction device as part of the heat source 50 of the subsequent thermal decomposition device 30. Reduce energy consumption.
  • the conductive water in the water conductive device reacts with the deactivated and discarded oxides to generate hydroxides, and the hydroxides and the carbon dioxide generated by decomposition of the thermal decomposition device 30 participate in the decomposition of the industrial solid waste ore. mineralization reaction of the system 40.
  • the conductive water in the water conduction device reacts with the deactivated and discarded calcium oxide to generate calcium hydroxide, and the calcium hydroxide and the thermal
  • the carbon dioxide produced by the decomposition of the decomposition device 30 participates in the mineralization reaction of the industrial solid waste mineralization system 40; optionally, when the first carbonate product is magnesium carbonate, the conductive water in the water conductive device and The deactivated and scrapped magnesium oxide reacts to generate magnesium hydroxide, and the magnesium hydroxide and the carbon dioxide generated by decomposition of the thermal decomposition device 30 participate in the mineralization reaction of the industrial solid waste mineralization system 40; optionally, when the When the first carbonate product is calcium magnesium carbonate, the conductive water in the water conductive device reacts with the deactivated and scrapped calcium magnesium oxide to generate calcium magnesium hydroxide, and the calcium magnesium hydroxide and the thermal decomposition device
  • the carbon dioxide produced by the decomposition of 30 participates in the mineralization reaction of the industrial solid waste mineralization system
  • the specific type of the first carbonate changes with the change of the adsorbent of the adsorption reaction device 20 .
  • the specific type of the second carbonate changes with the change of the industrial solid waste mineralization system 40
  • the composition of industrial solid waste varies.
  • the industrial solid waste mineralization system 40 includes: a mixing reaction device 41 and a solid-liquid separation device 42, wherein the deactivated and discarded oxides and the thermal decomposition device 30 minutes
  • the carbon dioxide produced by the decomposition is transported to the mixing reaction device 41 to participate in the reaction;
  • the solid-liquid separation device 42 is used to perform solid-liquid separation on the slurry reacted by the mixing reaction device 41, wherein the unprocessed solid-liquid separation obtained
  • the reacted solid particles will be recycled to the next stage of reaction and separation.
  • the industrial solid waste mineralization system 40 can make full use of the above-described deactivated and scrapped oxides as well as the carbon dioxide and industrial solid waste generated by the decomposition of the thermal decomposition device 30. After a series of reactions, separation and other processes, it can be obtained Target product - for example, calcium carbonate, magnesium carbonate or calcium magnesium carbonate, wherein the target product is modified based on the elements contained in the steel slag.
  • the industrial solid waste mineralization system 40 further includes: a product preparation device 43 for preparing target products based on the clear liquid separated by the solid-liquid separation device 42, wherein the separated clear liquid contains the target product. Ions - calcium ions, magnesium ions or a mixture of calcium and magnesium ions, and the target product is calcium magnesium carbonate, calcium carbonate or magnesium carbonate, etc.
  • This embodiment also includes: a recovery water circulation device 44.
  • the recovery water after the above-mentioned separated clear liquid is generated into the product is circulated to the mixing reaction device 41 through the recovery water circulation device 44, wherein the number of cycles of the recovery water is m ⁇ 2.
  • steel slag, auxiliary reagents and water are added to the mixing reaction device 41, and are continuously added in according to a certain proportion and fully mixed. After fully mixing, a slurry is obtained; carbon dioxide is continuously poured into the said mixing reaction device 41 under a certain pressure. The mixing reaction device 41 reacts with the slurry, and the mixing reaction device 41 continuously discharges the reacted slurry.
  • the steel slag can also be replaced by other industrial wastes, such as iron slag, fly ash, bottom ash, red mud, construction waste/waste cement, tailings, etc.; the steel slag can also be replaced by ore raw materials or tailings. Ore, the ore raw material includes calcium and magnesium ores.
  • the auxiliary reagent includes at least one acid or salt or composition of an organic acid radical, wherein the above-mentioned organic acid radical acid includes but is not limited to: oxalic acid, citric acid, picolinic acid, gluconic acid, glutamic acid, formic acid, acetic acid, propionic acid, etc. acid, butyric acid, valeric acid, lactic acid, succinic acid, phosphoric acid, pyrophosphate, ascorbic acid or phthalic acid.
  • organic acid radical acid includes but is not limited to: oxalic acid, citric acid, picolinic acid, gluconic acid, glutamic acid, formic acid, acetic acid, propionic acid, etc. acid, butyric acid, valeric acid, lactic acid, succinic acid, phosphoric acid, pyrophosphate, ascorbic acid or phthalic acid.
  • This embodiment eliminates the use of strong acids or highly corrosive acids (nitric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid) by adjusting the pressure of carbon dioxide, the ratio of auxiliary reagents, and the reaction temperature, thereby achieving continuous leaching of target components.
  • the slurry reacted by the mixing reaction device 41 undergoes at least one stage of solid-liquid separation treatment through the solid-liquid separation device 42, and the unreacted solid particles obtained by solid-liquid separation will be recycled as raw materials for the next stage of reaction. and separation.
  • the solid-liquid separation device 42 preferably adopts two-stage solid-liquid separation.
  • the solid-liquid separation device 42 includes: a first-level coarse separation unit and a second-level fine separation unit, wherein the first-level rough separation unit The unit is used to remove solid particles with a particle size of ⁇ 5-10 ⁇ m, and the secondary fine separation unit 40 is used to remove solid particles with a particle size of ⁇ 1-5 ⁇ m.
  • the optimized separation scheme for particles in different particle size ranges ensures that the separation equipment can stably and permanently perform continuous solid-liquid separation under optimal load conditions, effectively shortening the overall separation time and It extends the continuous and stable operation time of the separation system and effectively avoids the technical problems caused by single-stage separation.
  • the solid-liquid separation device 42 is also provided with a three-stage solid-liquid separation unit on the basis of the above-mentioned two-stage solid-liquid separation, using a disc centrifuge, a plate and frame filter press or a filter to perform continuous separation. Separate to continuously obtain a clear solution containing the target ions.
  • the ferric hydroxide precipitates are collected through enrichment, so that the above-mentioned relatively high iron elements can be reasonably and effectively recovered and utilized.
  • This application can couple CO 2 capture in flue gas with a CO 2 mineralization system based on industrial solid waste, in which the concentrated carbon dioxide and deactivated scrapped oxides generated during the carbon dioxide capture process in flue gas can be used to produce high-quality
  • the raw materials required for high-quality carbonates coupling the two processes not only realize the capture and utilization of carbon dioxide, but also realize the reuse of waste; while producing high-quality chemical products, the carbon dioxide capture production line in flue gas also It is easy to be organically combined with the production line of the carbon dioxide mineralization system based on industrial solid waste, which expands the selection range and acquisition methods of carbon dioxide sources for the carbon dioxide mineralization system based on industrial solid waste, and reduces the cost of carbon dioxide concentration and industrial solid waste. Waste carbon dioxide mineralization process costs. In summary, this application has good market application prospects.

Abstract

一种烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，包括：吸附反应装置（20），烟气输入吸附反应装置（20）中并与内置于吸附反应装置（20）中的吸附剂发生吸附反应，并生成第一碳酸盐产品；热分解装置（30），第一碳酸盐产品经热分解装置（30）热分解处理后生成氧化物及二氧化碳；氧化物重新返回至吸附反应装置（20）中循环反应；失活报废的氧化物被输送至工业固废矿化系统（40）中参与反应；二氧化碳被输送至工业固废矿化系统（40）中参与反应。

Description

烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统 技术领域
本申请属于湿法冶金技术、二氧化碳捕集、利用和封存(Carbon Capture,Utilization and Storage)、固废资源化利用领域，具体涉及烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统。
背景技术
常见的烟气中二氧化碳捕集方法，以钙循环法为例，是目前非常有行业前景的二氧化碳捕集的工艺流程，其优点在于既可以作为工厂烟气管道末端的二氧化碳捕集的解决方案，也可以和钢厂、电厂、水泥厂或石灰厂等集成建设；同时回收的CO2纯度较高，便于收集储存运输。钙循环法吸收CO2的核心原理是利用CaO和CO2反应的可逆性实现碳酸化/煅烧的持续循环，实现CO2的捕集。
CaO+CO2→CaCO3  ΔH＝-178kJ/mol
CaCO3→CaO+CO2  ΔH＝+178kJ/mol
目前，基于钙循环原理的CO2捕集技术多集中于水泥或石灰厂等的烟气中二氧化碳捕集，但是，针对钢厂烟气中二氧化碳捕集以及与如钢厂等相关产线的耦合仍然属于空白领域。同时，天然钙基吸附剂(如，石灰石等)在多次循环之后，氧化钙(CaO)的吸收能力会急剧下降，循环次数达到一定程度后的失活CaO无法继续作为高效CO2吸附剂。另外，失活CaO的处置方式也是比较棘手的问题，以水泥行业为例，失活CaO可以添加入原料进行水泥烧制；但是，在其他行业应用场景，就缺乏较好的失活CaO的利用方式。所以，通常的钙循环法如果为了维持较高的CO2捕集效率又不造成二次污染，就需要一种具有较高吸收能力和循环效率且产废不对环境造成二次污染的钙基吸附剂，此类高性能钙基吸附剂的价格通 常是企业普遍难以接受的。如果考虑吸附剂成本而使用传统吸附剂，则会导致捕集效率较低，产废量大且难以处理等问题。所以，钙循环法进行烟气中二氧化碳捕集的效率和成本一直是行业所面临的挑战。
发明内容
针对上述现有技术的缺点或不足，本申请要解决的技术问题是提供烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统。
为解决上述技术问题，本申请通过以下技术方案来实现：
本申请提出了烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，包括：
吸附反应装置，烟气输入所述吸附反应装置中并与内置于所述吸附反应装置中的吸附剂发生吸附反应，并生成第一碳酸盐产品；
热分解装置，所述第一碳酸盐产品经所述热分解装置热分解处理后生成氧化物以及二氧化碳；
工业固废矿化系统，所述氧化物重新返回至所述吸附反应装置中循环反应；循环反应多次后，失活报废的所述氧化物被输送至所述工业固废矿化系统中参与反应；所述二氧化碳被输送至所述工业固废矿化系统中参与反应。
可选地，上述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其中，所述工业固废矿化系统制备的第二碳酸盐产品可部分循环至所述热分解装置继续进行热分解处理形成新的吸附剂，以补充失活报废的氧化物。
可选地，上述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其中，还包括：匹配所述吸附反应装置设置的导热水装置，所述导热水装置用于收集所述吸附反应装置的热量。
可选地，上述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其中，所述导热水装置中的导热水与报废的所述氧化物反应生成氢 氧化物，所述氢氧化物以及经所述热分解装置分解产生的二氧化碳参与所述工业固废矿化系统的矿化反应。
可选地，上述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其中，所述热分解装置的热源采用传统化石燃料、太阳能、风能等可持续能源、核能或者钢渣回收余热。
可选地，上述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其中，采用传统化石燃料燃烧产生的二氧化碳被收集并输入所述吸附反应装置中参与吸附反应。
可选地，上述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其中，所述吸附剂包括：第一碳酸盐产品经热分解产生的氧化物、第二碳酸盐产品经热分解产生的氧化物、天然钙基吸附剂、天然镁基吸附剂或碱性工业固废。
可选地，上述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其中，还包括：脱硫装置，和/或，脱硝装置；所述烟气经所述脱硫装置和/或所述脱硝装置脱硫、脱硝处理后，被输送至所述吸附反应装置中。
可选地，上述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其中，所述工业固废矿化系统包括：混合反应装置以及固液分离装置，其中，失活报废的所述氧化物以及经所述热分解装置分解产生的二氧化碳被输送至所述混合反应装置中参与反应；所述固液分离装置用于对所述混合反应装置反应的浆料进行固液分离，固液分离所得的未反应的固体颗粒将循环至下一阶段的反应和分离。
可选地，上述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其中，所述工业固废矿化系统还包括：产物制备装置，基于经所述固液分离装置分离后的清液制备所述第二碳酸盐产品，所述第二碳酸盐产品部分循环至所述热分解装置，经热分解处理以补充失活报废的氧化物。
可选地，上述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦 合系统，其中，所述第一碳酸盐产品包括：碳酸钙、碳酸镁或碳酸钙镁；和/或，所述第二碳酸盐产品包括：碳酸钙、碳酸镁或碳酸钙镁。
与现有技术相比，本申请具有如下技术效果：
本申请能够将烟气中CO2捕集和基于工业固废的CO2矿化系统耦合，其中烟气中二氧化碳捕集过程中产生的提浓二氧化碳和失活报废的氧化物等可作为生产高质量碳酸盐所需要的原料，将两种工艺耦合既实现了二氧化碳的捕集和利用，又实现了废物再利用；生产出高质量的化工产品的同时，烟气中二氧化碳捕集产线也易与基于工业固废的二氧化碳矿化系统的产线进行有机地结合等，扩充了基于工业固废的二氧化碳矿化系统的二氧化碳来源的选择范围和获取方式，降低了二氧化碳提浓成本和工业固废二氧化碳矿化工艺成本。
本申请中的工业固废矿化系统制备的第二碳酸盐产品可部分循环至所述热分解装置中进行再次热分解，以补充失活报废的氧化物，从而形成双循环系统，相比于现有技术具有一定的优越性，该循环工艺能够充分利用现有工业固废中的钙镁元素，实现资源的重复利用；并且双循环工艺可保证反应过程的连续性，提高反应效率，优化二氧化碳捕集和利用的综合成本。
本申请中的导热水装置可吸收吸附反应装置的余热以作为工业固废矿化系统的部分热源，不浪费导热水，节能且经济。
本申请可实现固废和二氧化碳资源化循环利用，能够实现绿色再生，能够控制额外投入的物耗和能耗，几乎不产生二次污染，能够实现碳减排和利用，绿色环保。
附图说明
通过阅读参照以下附图所作的对非限制性实施例所作的详细描述，本申请的其它特征、目的和优点将会变得更明显：
图1：本申请一实施例烟气中二氧化碳捕集与基于工业固废的二氧化碳 矿化耦合系统的流程图；
图2：本申请另一实施例烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统的流程图；
图3：本申请一实施例中工业固废矿化系统的流程图。
具体实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
如图1所示，在本申请的其中一个实施例中，烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，包括：
吸附反应装置20，烟气10输入所述吸附反应装置20中并与内置于所述吸附反应装置20中的吸附剂发生吸附反应，并生成第一碳酸盐产品；
热分解装置30，所述第一碳酸盐产品经所述热分解装置30热分解处理后生成氧化物以及二氧化碳；
工业固废矿化系统40，所述氧化物重新返回至所述吸附反应装置20中循环反应；循环反应多次后，失活报废的所述氧化物被输送至所述工业固废矿化系统40中参与反应；所述二氧化碳被输送至所述工业固废矿化系统40中参与反应。
本实施例通过配置上述吸附反应装置20以及热分解装置30，能够将烟气中二氧化碳捕集法与工业固废矿化系统40进行耦合，即实现了二氧化碳的捕集和利用，同时又能生产出高质量的化工产品，同时烟气中二氧化碳捕集的产线也易与所述工业固废矿化系统40的产线进行结合等，工业化程度更高。
可选地，本实施例涉及的工业固废包括但不限于：钢渣、矿石原料或尾 矿、其他工业废弃物等，其中，所述矿石原料包括钙镁类矿石；其他工业废物包括：铁渣、粉煤灰、底灰、红泥、建筑垃圾/废旧水泥、尾矿等。
其中，在本实施例中，所述吸附剂可采用第一碳酸盐产品经热分解产生的氧化物、第二碳酸盐产品经热分解产生的氧化物、天然钙基吸附剂、天然镁基吸附剂或碱性工业固废，其中，所述天然钙基吸附剂包括但不限于：石灰石、白云石等。
进一步地，如图2所示，在申请的另一实施例中，所述工业固废矿化系统40制备的第二碳酸盐产品可部分循环至所述热分解装置30继续进行热分解处理，经热分解处理以补充失活报废的氧化物。本实施例是在上述实施例一的基础上增加了另一内循环工艺，该循环工艺能够充分利用现有工业固废中的钙镁元素，实现资源的重复利用；并且双循环工艺可保证反应过程的连续性，提高反应效率，优化二氧化碳捕集和利用的综合成本。
其中，上述涉及的第一碳酸盐产品包括：碳酸钙、碳酸镁或碳酸钙镁；所述第二碳酸盐产品包括：碳酸钙、碳酸镁或碳酸钙镁。
在本实施例中，当所述吸附剂以氧化钙为主时，钙循环法吸收CO2的核心原理是利用CaO和CO2反应的可逆性实现碳酸/煅烧的持续循环，循环反应式为：
CaO+CO2→CaCO3    ΔH＝-178kJ/mol
CaCO3→CaO+CO2    ΔH＝+178kJ/mol
上述CaO和CO2的反应是强放热的反应过程。
其中，当所述吸附剂以氧化镁为主时，还涉及以下循环反应式：
MgO+CO2→MgCO3    ΔH＝-1012kJ/mol
MgCO3→MgO+CO2    ΔH＝+1012kJ/mol
当所述吸附剂同时含有氧化钙和氧化镁时，则同时具有以上循环反应过 程。
其中，上述MgO和CO2的反应是强放热的反应过程。
进一步可选地，还包括：脱硫装置(图中未示意)，所述烟气10经所述脱硫装置脱硫处理后，被输送至所述吸附反应装置20中。
进一步地，本实施例还包括：脱硝装置(图中未示意)，所述烟气10经所述脱硝装置脱硝处理后，被输送至所述吸附反应装置20中。
进一步优选地，本实施例同时配置脱硫装置和脱硝装置，所述烟气10经所述脱硫装置以及脱硝装置分别处理后，被输送至所述吸附反应装置20中，其中，所述脱硫装置以及所述脱硝装置的先后顺序并不做限定。
所述吸附反应装置20优选地采用吸附塔，进一步优选地，所述吸附反应装置20采用流化床反应器。
其中，所述烟气10将所述脱硫装置和/或所述脱硝装置进入所述吸附反应装置20与CaO进行碳酸化反应生成CaCO3产品，所述CaCO3产品被输送至所述热分解装置30进行热分解处理。或者，所述烟气10将所述脱硫装置和/或所述脱硝装置进入所述吸附反应装置20与MgO进行碳酸化反应生成MgCO3产品，所述MgCO3产品被输送至所述热分解装置30进行热分解处理。或者，所述烟气10将所述脱硫装置和/或所述脱硝装置进入所述吸附反应装置20与氧化钙镁进行碳酸化反应生成碳酸钙镁产品，所述碳酸钙镁产品被输送至所述热分解装置30进行热分解处理。
在本实施例中，所述烟气10来自于电厂烟气、钢铁厂高炉、转炉、精炼炉、石灰窑炉烟气、煤化工尾气或石油化工尾气。
所述热分解装置30优选地采用高温煅烧炉，在本实施例中，优选地煅烧温度为400-900℃。所述第一碳酸盐产品于所述高温煅烧炉中进行高温煅烧处理，生成氧化物和CO2。其中，反应生成的氧化物可以重新回到所述吸附反 应装置20中循环反应，而在反应实际的排烟温度和压力下能够高效的吸收高纯度CO2，便于冷却液化压缩之后转运和存储。而当氧化物的吸附下降至报废后，失活报废的氧化物可被输送至所述工业固废矿化系统40中参与矿化反应。
其中，上述涉及的具体反应过程以所述第一碳酸盐产品的不同而不同。具体地，当所述第一碳酸盐产品为CaCO3产品时，所述CaCO3产品于所述高温煅烧炉中进行高温煅烧处理，生成CaO和CO2。其中，反应生成的CaO可以重新回到所述吸附反应装置20中循环反应，而在反应实际的排烟温度和压力下能够高效的吸收高纯度CO2，便于冷却液化压缩之后转运和存储。而当CaO的吸附下降至报废后，失活报废的CaO可被输送至所述工业固废矿化系统40中参与钢渣的矿化反应。
同样地，当所述第一碳酸盐产品为MgCO3产品时，所述MgCO3产品于所述高温煅烧炉中进行高温煅烧处理，生成MgO和CO2。其中，反应生成的MgO可以重新回到所述吸附反应装置20中循环反应，而在反应实际的排烟温度和压力下能够高效的吸收高纯度CO2，便于冷却液化压缩之后转运和存储。而当MgO的吸附下降至报废后，失活报废的MgO可被输送至所述工业固废矿化系统40中参与钢渣的矿化反应。
同理，当所述第一碳酸盐产品为碳酸钙镁时，所述碳酸钙镁产品于所述高温煅烧炉中进行高温煅烧处理，生成氧化钙镁和CO2。其中，反应生成的氧化钙镁可以重新回到所述吸附反应装置20中循环反应，而在反应实际的排 烟温度和压力下能够高效的吸收高纯度CO2，便于冷却液化压缩之后转运和存储。而当氧化钙镁的吸附下降至报废后，失活报废的氧化钙镁可被输送至所述工业固废矿化系统40中参与钢渣的矿化反应。
天然钙基吸附剂/镁基吸附剂在多次循环之后，其吸收能力会急剧下降。下面以天然钙基吸附剂为例对其原理进行解释说明：CaO碳酸化时首先CO2首先扩散到颗粒表面进行快速反应，同时经过颗粒表面的孔渗透，与较大的孔表面发生反应，上述过程即化学反应控制的快速反应阶段。随后，颗粒表面及孔内表面形成的CaCO3产物层阻碍内部CaO和CO2的反应，当产物层超过一临界厚度时反应就进入产物层扩散控制的慢速反应阶段。吸附剂颗粒在高温下反复煅烧，颗粒内部的晶粒溶合长大，吸附剂的表面积和孔容积不断变小，发生烧结。随着循环次数增多，烧结现象加剧，小孔减少，大孔增多，晶粒和晶粒之间融合，吸附剂颗粒坍缩，导致吸收能力持续下降。所以循环次数过多的失活的CaO无法继续作为高效CO2吸附剂。通常的钙循环法为了维持较高的CO2捕集效率，需要一种具有较高吸收能力和循环效率，价格低廉且产废不对环境造成二次污染的钙基吸附剂。但是，在本实施例中，该部分失效或报废的CaO可被输送至所述工业固废矿化系统40中参与钢渣的矿化反应，即，该部分失效或报废的CaO可以加以完美利用；并且避免了现有技术中，需要额外使用例如改性CaO等高性能吸附剂等技术缺陷。
在本实施例中，所述热分解装置30的热源50可采用传统化石燃料、太阳能、风能等可持续能源、核能或者钢渣回收余热。如若采用钢渣回收余热，则可充分利用所述工业固废矿化系统40的有用资源，更大程度地实现资源化重复利用。
为进一步实现资源化重复利用，并且可以有效地将产生的二氧化碳进行固定，可选地，本实施例采用传统化石燃料燃烧产生的二氧化碳可被收集并输入所述吸附反应装置20中参与吸附反应，其中，所述传统燃料包括但不限于：天然气、煤炭、石油等。
本实施例还包括：匹配所述吸附反应装置20设置的导热水装置(图中未示意)，所述导热水装置用于收集所述吸附反应装置20的热量。由于CaO和CO2的反应、MgO和CO2的反应均是一个强放热反应过程，其反应放出的热量可以用所述导热水装置加以利用作为后续所述热分解装置30的部分热源50，减少能耗。
进一步优选地，所述导热水装置中的导热水与失活报废的氧化物反应生成氢氧化物，所述氢氧化物以及经所述热分解装置30分解产生的二氧化碳参与所述工业固废矿化系统40的矿化反应。可选地，当所述第一碳酸盐产品为碳酸钙时，所述导热水装置中的导热水与失活报废的氧化钙反应生成氢氧化钙，所述氢氧化钙以及经所述热分解装置30分解产生的二氧化碳参与所述工业固废矿化系统40的矿化反应；可选地，当所述第一碳酸盐产品为碳酸镁时，所述导热水装置中的导热水与失活报废的氧化镁反应生成氢氧化镁，所述氢氧化镁以及经所述热分解装置30分解产生的二氧化碳参与所述工业固废矿化系统40的矿化反应；可选地，当所述第一碳酸盐产品为碳酸钙镁时，所述导热水装置中的导热水与失活报废的氧化钙镁反应生成氢氧化钙镁，所述氢氧化钙镁以及经所述热分解装置30分解产生的二氧化碳参与所述工业固废矿化系统40的矿化反应。
其中，所述第一碳酸盐的具体类型以所述吸附反应装置20的吸附剂的改变而改变，同样地，所述第二碳酸盐的具体类型以所述工业固废矿化系统40中工业固废的成分不同而不同。
如图3所示，所述工业固废矿化系统40包括：混合反应装置41以及固液分离装置42，其中，失活报废的所述氧化物以及经所述热分解装置30分 解产生的二氧化碳被输送至所述混合反应装置41中参与反应；所述固液分离装置42用于对所述混合反应装置41反应的浆料进行固液分离，其中，固液分离所得的未反应的固体颗粒将循环至下一阶段的反应和分离。其中，所述工业固废矿化系统40能够充分利用上述失活报废的氧化物以及所述热分解装置30分解产生的二氧化碳以及工业固废等，经过一系列的反应、分离等过程，可获得目标产物-如，碳酸钙、碳酸镁或碳酸钙镁，其中，所述目标产物是基于钢渣中所含有的元素而改变的。
进一步优选地，所述工业固废矿化系统40还包括：产物制备装置43，基于经所述固液分离装置42分离后的清液制备目标产品，其中，上述分离后的清液中含有目标离子-钙离子、镁离子或钙镁离子混合物，所述目标产品为碳酸钙镁、碳酸钙或碳酸镁等。
本实施例还包括：回收水循环装置44，上述分离后的清液生成产品后的回收水经所述回收水循环装置44循环至所述混合反应装置41，其中，所述回收水的循环次数m≥2。
进一步地，所述混合反应装置41中还添加有钢渣、辅助试剂以及水，按照有一定配比连续投入其中并充分混合，充分混合后获得浆料；将二氧化碳在一定压力下连续打入所述混合反应装置41并与所述浆料进行反应，所述混合反应装置41连续排出经过反应的浆料。其中，所述钢渣还可替换为其他工业废弃物，如，铁渣、粉煤灰、底灰、红泥、建筑垃圾/废旧水泥、尾矿等；所述钢渣还可替换为矿石原料或尾矿，所述矿石原料包括钙镁类矿石。
所述辅助试剂包括至少一种有机酸根的酸或者盐或组合物，其中，上述有机酸根的酸包括但不限于：草酸、柠檬酸、吡啶甲酸、葡萄糖酸、谷氨酸、甲酸、乙酸、丙酸、丁酸、戊酸、乳酸、琥珀酸、磷酸、焦磷酸、抗坏血酸或酞酸。本实施例通过调节二氧化碳的压力、辅助试剂的配比和反应温度，免除了强酸或高腐蚀性酸(硝酸、盐酸、硫酸、氢氟酸)的使用，实现了对目标成分的连续浸取。
将所述混合反应装置41反应后的浆料经所述固液分离装置42经过至少一级固液分离处理，固液分离所得的未反应的固体颗粒将循环用作原料进行下一阶段的反应和分离。
其中，所述固液分离装置42优选地采用两级固液分离，具体地，所述固液分离装置42包括：一级粗分离单元以及二级细分离单元，其中，所述一级粗分离单元用于去除粒径≥5-10μm的固体颗粒，所述二级细分离单元40用于去除粒径≤1-5μm的固体颗粒。通过上述多级分离，针对不同粒径区间的颗粒进行优化的分离方案，保证了分离设备能够稳定、持久地在最佳负荷条件下进行连续固液分离，有效地缩短了整体分离时间的缩短且延长了分离系统连续稳定运行时间，有效避免了单级分离所带来的技术问题。
进一步优选地，所述固液分离装置42在上述两级固液分离的基础上还设置有三级固液分离单元，采用碟片式离心机、板框压滤机或过滤器等进行不间断分离以连续获得含有目标离子的清液。
其中，当经所述三级固液分离单元分离后清液含有较高的铁元素时，通过富集收集氢氧化铁沉淀，从而对上述较高的铁元素进行合理有效地回收和利用。
本申请能够将烟气中CO2捕集和基于工业固废的CO2矿化系统耦合，其中烟气中二氧化碳捕集过程中产生的提浓二氧化碳和失活报废的氧化物等可作为生产高质量碳酸盐所需要的原料，将两种工艺耦合既实现了二氧化碳的捕集和利用，又实现了废物再利用；生产出高质量的化工产品的同时，烟气中二氧化碳捕集产线也易与基于工业固废的二氧化碳矿化系统的产线进行有机地结合等，扩充了基于工业固废的二氧化碳矿化系统的二氧化碳来源的选择范围和获取方式，降低了二氧化碳提浓成本和工业固废二氧化碳矿化工艺成本。综上，本申请具有良好的市场应用前景。
以上实施例仅用以说明本申请的技术方案而非限定，参照较佳实施例对本申请进行了详细说明。本领域的普通技术人员应当理解，可以对本申 请的技术方案进行修改或等同替换，而不脱离本申请技术方案的精神和范围，均应涵盖在本申请的权利要求范围内。

Claims (11)

  1. 烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其特征在于，包括：
    吸附反应装置，烟气输入所述吸附反应装置中并与内置于所述吸附反应装置中的吸附剂发生吸附反应，并生成第一碳酸盐产品；
    热分解装置，所述第一碳酸盐产品经所述热分解装置热分解处理后生成氧化物以及二氧化碳；
    所述工业固废矿化系统，所述氧化物重新返回至所述吸附反应装置中循环反应；循环反应多次后，失活报废的所述氧化物被输送至所述工业固废矿化系统中参与反应；所述二氧化碳被输送至所述工业固废矿化系统中参与反应。
  2. 根据权利要求1所述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其特征在于，所述工业固废矿化系统制备的第二碳酸盐产品可部分循环至所述热分解装置继续进行热分解处理，以补充失活报废的所述氧化物。
  3. 根据权利要求1所述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其特征在于，还包括：匹配所述吸附反应装置设置的导热水装置，所述导热水装置用于收集所述吸附反应装置的热量。
  4. 根据权利要求3所述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其特征在于，所述导热水装置中的导热水与报废的所述氧化物反应生成氢氧化物，所述氢氧化物以及经所述热分解装置分解产生的二氧化碳参与所述工业固废矿化系统的矿化反应。
  5. 根据权利要求1所述的烟气中二氧化碳捕集与基于工业固废的二氧化 碳矿化耦合系统，其特征在于，所述热分解装置的热源采用传统化石燃料、太阳能、风能、核能或者钢渣回收余热。
  6. 根据权利要求1所述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其特征在于，采用传统化石燃料燃烧产生的二氧化碳被收集并输入所述吸附反应装置中参与吸附反应。
  7. 根据权利要求1所述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其特征在于，所述吸附剂包括：第一碳酸盐产品经热分解产生的氧化物、第二碳酸盐产品经热分解产生的氧化物、天然钙基吸附剂、天然镁基吸附剂或碱性工业固废。
  8. 根据权利要求1所述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其特征在于，还包括：脱硫装置，和/或，脱硝装置；所述烟气经所述脱硫装置和/或所述脱硝装置脱硫、脱硝处理后，被输送至所述吸附反应装置中。
  9. 根据权利要求1所述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其特征在于，所述工业固废矿化系统包括：混合反应装置以及固液分离装置，其中，失活报废的所述氧化物以及经所述热分解装置分解产生的二氧化碳被输送至所述混合反应装置中参与反应；所述固液分离装置用于对所述混合反应装置反应的浆料进行固液分离，固液分离所得的未反应的固体颗粒将循环至下一阶段的反应和分离。
  10. 根据权利要求9所述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其特征在于，所述工业固废矿化系统还包括：产物制备装置，基于经所述固液分离装置分离后的清液制备所述第二碳酸盐产品，所 述第二碳酸盐产品至少部分循环至所述热分解装置，经热分解处理以补充失活报废的氧化物。
  11. 根据权利要求1至10任一项所述的烟气中二氧化碳捕集与基于工业固废的二氧化碳矿化耦合系统，其特征在于，所述第一碳酸盐产品包括：碳酸钙、碳酸镁或碳酸钙镁；和/或，所述第二碳酸盐产品包括：碳酸钙、碳酸镁或碳酸钙镁。
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